Recent advances in the structural design and regulation of lanthanide clusters: Formation and self-assembly mechanisms

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 493, P. 215322 - 215322

Published: July 4, 2023

Language: Английский

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Self-Assembly Bifunctional Tetranuclear Ln₂Ni₂ Clusters: Magnetic Behaviors and Highly Efficient Conversion of CO₂ under Mild Conditions

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(38), P. 15098 - 15107

Published: Sept. 12, 2022

A series of heterometallic tetranuclear clusters, Ln2Ni2(NO3)4L4(μ3-OCH3)2·2(CH3CN) (Ln = Gd(1), Tb(2), Dy(3), Ho(4), Er(5); HL methyl 3-methoxysalicylate), were synthesized solvothermally. The intramolecular synergistic effect two metal centers Ln(III) and Ni(II) the exposed multimetallic sites serving as Lewis acid activators greatly increase efficiency CO2 conversion, yield for cluster 3 can be achieved at 96% atmospheric pressure low temperature. In particular, self-assembly multimetal center with polydentate ligand shows good generality enhanced recyclability. design such 3d-4f clusters provides an effective strategy conversion under greener conditions. Meanwhile, magnetic investigations indicate that 1 is a candidate refrigerant materials relatively large magnetocaloric (MCE) (-ΔSm 28.5 J kg-1 K-1 3.0 K 7.0 T), single-molecular magnet behavior zero dc field. Heterometallic special properties catalytic are rare. Thus, they potential bifunctional applied in practice.

Language: Английский

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Magnetic materials based on heterometallic Cr^II/III–Ln^III complexes

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(15), P. 4322 - 4357

Published: Jan. 1, 2023

Exchange interaction plays a pivotal role in dictating the single-molecule magnet (SMM) behaviour heterometallic complexes. This review covers SMM and magnetocaloric effects of Cr( iii )–Ln( )-based

Language: Английский

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Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Oct. 24, 2024

Heterometallic cluster-based materials offer the potential to incorporate multiple functionalities, leveraging aggregation effects of clusters and translating this heterogeneity complexity into unexpected properties that are more than just sum their components. However, rational construction heterometallic remains challenging due metal cation coordination structural unpredictability. This minireview provides insights a general synthetic strategy based on Hard Soft Acids Bases (HSAB) theory, summarizing its advantages in designed synthesis discrete (intracluster assembly) infinite (intercluster assembly). Furthermore, it emphasizes exploit intrinsic mixed components achieve breakthroughs across broad range applications. The from review expected drive progress controllable predictable manner.

Language: Английский

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Water-Stable Al₃Ni₄ Polynuclear Heterometallic Compound for Near-Infrared Photothermal Conversion

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

In this paper, a polynuclear heterometallic compound (H3O)[Al3Ni4(OH)6(MBA-NO2)6(H2O)6] (Al3Ni4, H2MBA-NO2 = 2-hydroxy-3-methoxy-5-nitrobenzoic acid) with seven-star disk metal core has been synthesized by the solvothermal method. Al3Ni4 good stability in water and several organic solvents, its solid powder shows photothermal effect under 980 nm laser irradiation, temperature can reach 138.8 °C within 100 s 1.0 W cm-2 power irradiation. Considering effect, evaporation of was measured. It be further used as material seawater evaporation.

Language: Английский

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Electrospray Ionization Mass Spectrometry Insights into the Assembly of Lanthanide-Containing Clusters

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

ConspectusAtomically precise metal clusters with well-defined crystal structures have emerged as a rapidly growing field within coordination and materials chemistry. Among them, lanthanide-containing (LCCs) are particularly notable for their aesthetically pleasing architectures intriguing properties. Achieving synthesis accurate structural characterization of these is crucial unlocking potential applications. Mass spectrometry (MS), electrospray ionization mass (ESI-MS), has proven to be powerful tool, providing exceptional sensitivity clarity in revealing the formation mechanisms details clusters. In this Account, we explore synthesis, characterization, assembly LCCs utilizing ESI-MS. We begin by tracing historical development LCCs, emphasizing critical role single-crystal X-ray diffraction confirmation challenges associated it. then discuss application ESI-MS characterizing highlighting how technique can monitor processes determine molecular weights charge states. introduce difference fingerprint isomorphism (MDFI) method, which facilitate rapid analysis LCCs' data. Furthermore, state solution characterization. By ESI-MS, enhance understanding propose new strategies designing synthesizing tailored functions. Looking forward, method will play increasingly significant roles LCC research. The continued technologies deepen structure-property relationships. With ongoing convergence computational chemistry information science, anticipate more design leading broader applications magnetism, optics, catalysis.

Language: Английский

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Impact of 3d Metal Ions on the Magnetic Dynamics in Isostructural Tetranuclear Butterfly {Ni₂^IIDy₂^III} and {Co₂^IIDy₂^III} Complexes

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(15), P. 6492 - 6502

Published: July 25, 2024

This paper describes the synthesis, structures, and magnetic properties of four isostructural butterfly-type heterometallic tetranuclear 3d-4f complexes, [Ni2Dy2(HL1)2(μ3–OH)2(piv)6]·2CH3CN (1), [Ni2Dy2(HL2)2(μ3–OH)2(piv)6]·2CH3CN (2), [Co2Dy2(HL1)2(μ3–OH)2(piv)6]·2H2O (3), [Co2Dy2(HL2)2(μ3–OH)2(piv)6]·2CH3CN (4), derived from two closely related Schiff base ligands H2L1 H2L2 in presence pivalate (piv) ions. X-ray crystallographic studies 1–4 revealed that all complexes are constructed with a type-II butterfly core which DyIII ions located at body positions, while 3d metal (NiII CoII) occupy wingtip positions. It is noteworthy reported systems containing NiII CoII have been isolated as type-I only one report each on Ni2IIDy2III Co2IIDy2III systems, both structurally magnetically characterized. Direct current susceptibility measurements performed response dominated by depopulation Stark sublevels ZFS cations case 3 4 weak intramolecular superexchange interactions calculated means CASSCF CASSCF/NEVPT2 calculations. Dynamic analogues (3 4) display single-molecule magnet behaviors additional anisotropy centers responsible for occurrence out-of-phase contrast to 1 2 poorly anisotropic cations.

Language: Английский

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Different anion (NO₃⁻ and OAc⁻)-controlled construction of dysprosium clusters with different shapes

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(12), P. 5665 - 5675

Published: Jan. 1, 2024

The complex hydrolysis process and strong uncertainty of self-assembly rules have led to the precise synthesis lanthanide clusters still being in "blind-box" stage simplifying developing reliable regulation strategies attracted widespread attention. Herein, different anions are used induce construction a series dysprosium with shapes connections. When selected anion is NO

Language: Английский

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Structure and assembly studies of two planar Dy(iii) single molecule magnets with double relaxations

Journal of Materials Chemistry C, Journal Year: 2024, Volume and Issue: 12(11), P. 4093 - 4102

Published: Jan. 1, 2024

We presented here the assembly mechanisms of two planar tetranuclear Dy 4 and hexanuclear 6 single molecule magnets with double relaxations.

Language: Английский

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Alkoxy-Bridged Dicopper(II) Cores Meet Tetracyanonickelate Linkers: Structural, Magnetic, and Theoretical Investigation of Cu/Ni Coordination Polymers

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(14), P. 6053 - 6064

Published: April 2, 2024

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2(Hbdea)2Ni(CN)4]n (1) and [Cu2(dmea)2Ni(CN)4]n·nH2O (2), were successfully self-assembled in water by reacting Cu(II) nitrate with H2bdea (N-butyldiethanolamine) Hdmea (N,N-dimethylethanolamine) the presence of sodium hydroxide [Ni(CN)4]2–. These new polymers investigated single-crystal powder X-ray diffraction fully characterized FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, theoretical DFT CASSCF calculations. Despite differences crystal systems, both compounds, each dinuclear building block [Cu2(μ-aminopolyalcoholate)2]2+ is bridged diamagnetic [Ni(CN)4]2– linkers, resulting 1D or 2D (2) metal–organic architectures. Experimental studies show that compounds display strong antiferromagnetic coupling (J = −602.1 cm–1 for 1 −151 2) between ions within dimers mediated μ-O-alkoxo bridges. results are corroborated broken symmetry studies, which also provide further insight into electronic structures copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be model to widen still limited family Cu/Ni polymer materials different functional properties.

Language: Английский

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